Electronic Modulation and Symmetry‐Breaking Engineering of Single‐Atom Catalysts Driving Long‐Cycling Li−S Battery

Abstract Developing efficient and durable single‐atom catalysts is vitally important for the sulfur redox reaction (SROR) in Li−S battery, while it remains enormous challenging. Herein, undercoordinated Ni−N 3 moieties anchored on N,S‐codoped porous carbon (Ni−NSC) is obtained to enhance the SROR. The experiments and theoretical calculations indicate that the symmetry‐breaking charge transfer in Ni single‐atom catalyst originates from tuning effect of sulfur atoms mediated Ni−N 3 moieties, which can both facilitate the chemical adsorption by formation of N−Ni⋅⋅⋅S n 2− , and achieve a rapid redox conversion of polysulfides because of the enhanced electron transfer. As results, the Ni−NSC based Li−S battery delivers a very high initial reversible capacity (1025 mAh g −1 at 1 C), as well as outstanding cycling‐stability for 2400 cycles at 2 C and 3 C, respectively. Noteworthy, the areal capacity can reach 7.8 mAh cm −2 at 0.05 C and a retention capacity of 4.7 mAh cm −2 after 100 cycles at 0.2 C for Ni−NSC based Li−S battery with sulfur loading of 5.88 mg cm −2 . This work provides profound insight for rational optimizing microscopic electronic density of active site to promoting SROR in metal‐sulfur batteries.